JPS58173162A - Novel cumarine, manufacture and use as dye - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The subject of the invention is a compound of the general formula (1) (wherein X is optional) one or more fluorine, one chlorine or bromine atoms or one or more alkyl o1-c4.a ″3
Kishika Ryo Q. Shea7-・-to0-・Amino-・Monoalkyl 01 a, Amino-・Dialkyl. 1-04 amino-, monoarylamino-, diarylamino-, carbonyl-, carbonamide-, carbon+noalkyl a
l-c4 amido-, carbonyl-c1-04 amido-, alkoxy-al-c4carbonyl- or phenyl residues substituted by trifluoromethyl groups or optionally e.g. chlorine or bromine atoms or alkyl Thiophene-, pyridine- substituted with IτG or nitro group
, naphthalene or pyrene residue, and Y is a hydrogen atom or cyan or alkoxy. 1-o4 carbonyl group,
Optionally, for example, fluorine, chlorine or bromine atoms or alkyl, alkoxy, nitro, amia, -C4, monoalkyl. Phenyl residues substituted by 1-o4 amino- or dialkyl-positioned 7-amino groups or optionally quaternized and optionally e.g. fluorine-5 chlorine- or bromine atoms or alkyl, alkoxyc1-. 4,
Nitro-, cyclo-, or alkyl carboxylate. , -04 Thiophene-, benzothio7ene-, 7 substituted by ester group
Ran-, benzo7ran-, imitazole-, benzimidazole-, thiazole-, benzothiazole-, oxazole- or pendioquinazole residues are 6, 2 means a hydrogen atom or a carboxylic acid amide- or cyan group,
R is hydrogen-1 fluorine-5 chlorine- or bromine atom or
・A'7'cl-c4' = o-'1-a4 amino-, monoarylamino-, sia-1-c4-ruxy.1-04 amino- or cyan group, and n
(indicates the number 1 or 2) and its production method, and this compound can be used as a dye in synthetic fiber materials such as cellulose-G, 2-
or synthetic resins for dyeing or printing fiber materials consisting of triacetates, polyamides, polyurethanes, polycarbonates or especially linear polyesters, optionally present in admixture with natural fiber materials, such as cellulose fibers or wool. and for the melt-spinning dyeing of polyesters, especially polyethylene terephthalate, and the use of the compounds in light collection systems.

The dye of the general formula (1) above is a dye of the general formula (2) (wherein X, R
and n have the above meanings and M is a chlorine or bromine atom. It is condensed with a compound represented by cyano- or alkoxy carbonyl group) by a method known per se, and in this case, the obtained general formula (4) % formula % (wherein, m, 1, !, Y, R and n have the above-mentioned meanings) with a non-oxidizing aqueous mineral acid, preferably sulfuric acid or diphosphoric acid-60 (i-900f/KIIfE or yo
The concentration of u-asov/- is 80! The above general formula (1
) in which Z=H-O is converted into a compound KJj and optionally processed by methods known per se (German Patent Application No. 28
No. 44299') with a dicyanide salt and the addition compound formed in this case as intermediate product is simultaneously or subsequently reacted with a dicyanide in a manner known per se with a dicyanide salt, in which Z = ON of the general formula (1). - in the general formula (1), Z = 0O-III! - It can be produced by saponifying the compound.

The compound of general formula (2) above can be prepared by the method described in European Patent Application Publication No. 4522.
Vilam 'o-3(211)-inoquinoline derivatives
aier-1iaaak-complex and preferably 0 to 50
It can be produced by reacting at a temperature of °C.

The condensation of the adehyde of the above general formula (2) with the above general formula (to)) is carried out under KnO.v@nagex condensation conditions or by reaction with a strong organic or inorganic base under a catalyst in a polar solvent. . Suitable solvents in this case are lower aliphatic alcohols such as methanol, ethanol or gropanol and nitrogen-containing solvents such as pyridine, picoline, dimethylformamide or N-methylpyrrolidone. Bases include alkali metal hydroxides such as potassium hydroxide or sodium hydroxide, also alkali metal alcoholates such as sodium metal-F1 potassium metalate, sodium etallate or potassium etallate and nitrogen bases such as piperidine, pyrrolidone or N-methyl. It is aniline. The reaction is carried out at 0-80°C, preferably 220-60x
The nosvena.1-reaction is preferably carried out in a nonpolar solvent in the presence of an inorganic or organic condensing agent at a temperature of 50-150 DEG C., preferably 9Q-120 DEG C., with simultaneous removal of the water of reaction. Hydrocarbons such as benzene, toluene,
Suitable are xylene or hexane, chlorinated hydrocarbons such as chlorobenzate or chloroform, or esters of organic acids such as methyl acetate or ethyl acetate-F.

Suitable condensing agents are nitrogen bases such as piperidine, pyrrolidine or 1-methylaniline and salts of nitrogen bases such as piperidine and ammonium acetate.

The compound of z=cii- in the formula (1) above can be obtained by converting the compound of the general formula (1) with Z=H- by a method known per se, for example, the method described in German Patent Application No. 811112844299. It can be prepared by reaction with a cyanide salt in a dusting agent and simultaneous or subsequent treatment of the addition compound formed as an intermediate with a quaternizing agent.

The cyanide salts used are preferably water-soluble alkali cyanides, such as sodium or potassium cyanide, optionally used as solids or especially in the form of concentrated aqueous solutions.

Suitable solvents are polar Im solvents such as alcohols such as methanol, ethanol, ingropanol or ethylene glycol, and especially aprotic dipolar solvents such as dimethylformamide, pyridine or picoline.

The reaction with the cyanide salt is carried out at 0-100°C, preferably at 5-100°C.
y3゜. The oxidation of the addition compound obtained as an intermediate product is carried out at a temperature of -10 to +30°C, preferably -
It is carried out in the range of 5 to +10°C.

For oxidizing the addition compounds obtained as intermediates, oxidizing agents such as hydrogen peroxide, persulfates or organic peroxides such as dibenzoyl peroxide, as well as nitric acid, bromine or lead acetate, are suitable.

The novel azacoumarin of general formula (1) is a yellow to dot colored crystalline powder, which exhibits red fluorescence and sm in organic solvents, such as red fluorescence.

The new marine compounds, alone or in admixture with each other or with other O dyes, are preferably in the form of formulations, for example aqueous dispersions or solutions or emulsions or dispersions in organic solvents - this may be in solvents or in solvent mixtures. Synthetic fiber materials that can still contain water, such as cellulose sioux, etc.
or - fibrous materials consisting of trioxytate, polyamides such as poly-1-caglolactam or polyhexamethylene diamine adibate)/2>, furthermore fibrous materials consisting of polyurethanes or polycarbonates, and in particular fibers consisting of linear polyesters such as polyethylene terephthalate. They are suitable for dyeing or printing materials, which can be present in admixture with natural fiber materials, for example cellulose fibers or wool-based fiber materials, respectively. In this case, the fiber materials can be present in various processing states, for example as tops, flocks, threads, woven or knitted fabrics.

It can also be carried out using an organic solvent. Dispersion of the dye can be carried out, for example, by trituration in the presence of a dispersant such as formaldehyde and a condensation product of technical m-cresol and sodium bisulfite, which has been neutralized with sulfuric acid. In other respects, the dyeing conditions depend on the type of synthetic fiber material present and its processing.

nt is the dyeing of the molded product made of cellulose acetate 7
Cellulose triacetate fibers processed in the temperature range of 5 to 85°C are approximately ? Dyeing is carried out at temperatures between OJF' and 125°C.

Dye O application on polyamide fiber material is about 90 to 120
It is carried out at a temperature of °C. For the dyeing of textile materials consisting of polyester, it is noted that the textile materials are dyed in the presence of a carrier such as 〇- or p-phenylphenol, methylnaphthalene or methyl salicylate at a temperature of 100° C. to about 150″ CO. It is utilized by dyeing at correspondingly high temperatures, e.g. application and heating action, e.g. by steam or dry heat) from about 3 to 3
It can be carried out so as to be fixed at a temperature in the range of about 106 to 230° C. for 0 minutes. The material dyed in this way is then preferably freed of adhering dye at the surface, for example by rinsing or reductive treatment, in order to improve its abrasiveness. This work-up is generally carried out at 60 DEG to 120 DEG C. in an aqueous treatment solution containing caustic Noda solution, Fium dithionite and a nonionic detergent such as an ethylene oxide-7 eno-adduct.

For dyeing synthetic fiber materials from organic solvents, e.g. at room temperature or higher, preferably at 70-130° C.)
The indenter dye is carried out either by exhaustion onto the fibers from a solution, or in a continuous process the woven or knitted fabric is impregnated with the dye solution, dried and subjected to a short heating action, for example at a temperature of 180 to 210°C. It can be implemented as shown below. Examples of solvents for the exhaustion method include 4o to 1, which are immiscible with water.
701: Solvents having an ID boiling point such as aliphatic halogen hydrocarbons such as methylene chloride, trichloroethane, trichlorethylene or trifluorotricumylethane. Particularly for continuous dyeing, water-miscible solvents such as alcohol or dimethylpolamide are also suitable. The solvent is of course also present as a mixture and can furthermore contain auxiliaries soluble in the solvent, such as fatty alcohols, alkylphenoyls or oxyalkylation products of fatty acids.

For forming prints on synthetic fiber materials, such as those made of polyester, polyamide or cellulose triacetate, the dyes can be used in the form of water-containing formulations, which in addition to finely dispersed dyes may contain excessive thickening agents. Fixation is done at atmospheric pressure after printing and drying or under high pressure up to 2-5 atm gauge at 10-f
It is performed without heat for 40 minutes. Similarly, fixing can be carried out by applying hot air at 140 to 12° C. for 38 seconds to 10 minutes.

Additionally, the dyes according to the invention can be applied to synthetic resins such as polyvinyl chloride, polyolefins or polystyrene OI! [Suitable for liquid coloring and lacquer melt spinning dyeing of polyesters such as polyethylene tere 7 tare.]

With the help of the new azacoumarine, some of the above textile materials can be dyed in very bright greenish yellow to navy blue colors. The dyeing is distinguished by high tinting strength, good build-up and adsorption capacity and good overall tenacity.

Furthermore, the new Marine hardware is also solid as well as optical concentrator.
r) Can be used in liquid form and dissolved in a solvent. Such light collection systems can be used in combination with optical elements as solar cells and in fluorescence-activated display elements.

The parts mentioned in the examples below mean parts by weight.

Example 1 2 parts of 1-phenyl-3-chloro-4-formylisoquinoline 8a were placed in a water separator for 2 hours in 312 parts of 2-cyanmethyl-6-dimethyl-penzoquinazole and 3 parts of ammonium acetate and 350 parts of benzene. Heat to reflux. The resulting reaction product was filtered with suction at 5°C, dried and
-Stir at 120°C for 2 hours in 300 parts of sulfuric acid. The resulting reaction mixture is poured onto 1000 parts of stirred sewage water, adjusted to pH 6 with 30 parts by weight of caustic soda, filtered with suction, washed with water to remove the sulfate and dried in vacuo at 100° C. to constant weight (71 Department). 57.9 parts (71 theoretical) of the compound N,M-dimethylform are obtained in the form of yellow crystals with a melting point >300 DEG C., which dye polyester fiber materials in a bright green-yellow shade.

Example 2 l-(4-diethylaminophenyl)-3-chloro-4
- 357 parts of formylisoquinoline, 17.4 parts of 2-cyanmethylbenzothiazole and 1 part of piperidine acetate
150 parts of toluene for 1 hour under reflux in a water separator.

The resulting condensation product is filtered with suction at 5 DEG C., dried and concentrated for 2 hours at 120 DEG C. in a 10-port 80-phosphorous H bath. The cooled reaction mixture was poured onto 300 parts of stirred sewage water, adjusted to pH 6-7 with 30% by weight caustic Noda solution, filtered with suction, washed with water to remove sulfate and concentrated in vacuo at 100° C. to constant weight. Dry (40 parts). After recrystallization from dimethylformamide, 30 parts of the compound (theoretical value 63-) has a melting point of 25
B-260'CO is obtained in the form of a black metallic shine needle-autumn material, which dyes polyester fiber materials in a clean, bright fluorescent red shade.

Example 3 1-phenyl-3-riwa-4-formyluia+J')
2 & 7 parts and 'Benzylcyani)' 177 parts to 30
46 parts of eusodium ethalate solution and 2 parts of methanol
Stir in 50 parts for 24 hours at room temperature. Add 1 part of the reaction mixture to 1 part of water.
Pour over 1,000 parts, adjust the pH to 3f with 2N HO, filter with suction, wash with water to remove the tetra-lide and dry in vacuo to constant weight at 1,001. quenched in 200 parts of sulfuric acid at 120°C for 6 hours,
Pour onto 1000 parts of water, filter with suction, wash with water to remove the sulfate and dry in vacuo at 100° C. to constant weight (30 parts).

After recrystallization from dioxane, 18 parts (51% of the theoretical value) of the compound represented by the formula had a melting point of 25
Obtained in the form of yellow crystals at 7-258°C, which dye polyester fiber materials in a fluorescent green color.

If carried out analogously to Examples 1-5 above, the following two Tables Examples 4-58 give rise to further dyes according to the invention as listed in the Tables below:
General formula of the dye: Example 59 41.8 parts of the dye prepared according to Example 1 were suspended in 500 parts of dimethylformamide, and a solution containing 152 parts of potassium cyanide in 40 parts of water was heated at 0-5°C. Add dropwise. After stirring for 5 hours at room temperature, 17.6 parts of bromine are subsequently added dropwise at 0 DEG to 5 DEG C. After standing for 5 hours, the reaction product was filtered with suction, washed with water to remove the f-bromide, and
Dry in vacuo at °C. After recrystallization from chlorobenzene, 1 part of the product 3α (48% of theory) has a melting point of 2.
It is obtained in the form of bright red crystals at 64-266° C., which dye polyester fibers in a reddish-yellow shade.

Example 60 47.7 parts of the dye prepared according to Example 2 are suspended in 55 Qlll of dimethylformamide and a solution of 152 parts of potassium cyanide in 40 parts of water is added dropwise at 0 DEG -5 DEG C. After stirring for 10 hours at room temperature under inert gas, 17.6 parts of bromine are subsequently added dropwise at a temperature of -5 DEG to +5 DEG C. After standing for 5 hours, the product is filtered with suction, washed with water to remove the Xiang bromide and dried at 80° C. in vacuo.

After recrystallization from dimethylformamide, 246 parts (theoretical value of 53 parts) of the product shown by the formula had a melting point of 247-24-9°C.
It is obtained in the form of black crystals, which dye polyester fibers in a Neigh blue shade.

Example 98 4.4 parts of the dye prepared according to Example 59 are mixed with 20 parts of concentrated sulfuric acid and 20 parts of concentrated sulfuric acid.
Stir for 4 hours at 25°C. The precipitated product is filtered off with suction, washed neutral with water and dried at 80° C. in vacuo. Orange dye powder with a melting point of 213-215°C as shown by the formula! L2
(theoretical value of 69 嗟) is obtained.

Agent Hikaru Esaki''-7, ゛、dan′・−

Claims (1)

[Claims] t General formula (1) (wherein X is optionally 1 or some fluorine, 1 chlorine, or bromine atom, or 1 or some alkyl□, alkoxy□,
Cyan-22Cl-04al-c4 Draw, Amino-, Monoarylamino 1-c4 No, Dialkyl〒100 Amino-, Monoarylamino-
, diarylamino-, carbonyl-, carbonamide-, carbonmonoalkyl □ amido 1 left carbon dialkyl 1-c4 ■ T-cho amido, alphoxy τF possible carbonyl- or trifluoromethyl group) substituted phenyl residue or case Yoshichlorine or bromine atom or alkyl ol -0
, or a nitro group) and substituted with a 9thio7ene, pyridine, naphthalene, or pyrene residue; 1 chlorine- or bromine atom or alkyl□, alkoxy+, , , al
,-c. ol -o4, phenyl residues substituted by nitro-, amino-, monoarylamino- or diarylamino o1- a4 01- o4 groups or optionally quaternized and optionally fluorine-1 chlorine - or a bromine atom or an alkyl □, aru a, -o4 koxy, nitro-, cyan- or alkyl zenate. 1-64 thiophene, benzothio7ene, 7rane, benzo7rane, imitasol, benzimidazole, thiazole, benzothiazole, oxazole, or benzoxazole residue substituted with 1-64 ester group, 2 R means a hydrogen atom, a carboxylic acid amide, or a cyanide group, and R is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an alkyl alkoxyat-o4'nide cl-c4, amino, monoalkyl0t-0 , amino-, diarylamino- or cyanogen group o1-c4, l and n represents a number of 1 or 2). Azakumarin according to claim 1, which is represented by formula 2. Azakumarine according to claim 1, which is represented by the following formula. Azakumarin according to claim 1, which is represented by formula 4. Azakumarin according to claim 1, which is represented by formula 1. Azakumarine according to claim 1, which is represented by the formula %). Azakumarin according to claim 1, which is represented by formula 1. a General formula (1) (in the formula, X is 1 or some fluorine-1 chlorine- or bromine atom or 1 or some alkyl ・Al3xio1-a4・sia:/-・=o, -o4 F rho, amino-, monoalkyl., -o4amino-,
Dialkyl. 1-(4amino-17noarylamino-
, diarylamino-, carbonyl-, carbonamido-, carbonmonoalkyl□amido-, carbondialkyl1-c4 amido-ar'7x0l-04carbo'o, -o
4 A phenyl residue substituted with a ru- or trifluoromethyl group or optionally a chlorine- or bromine atom or an alkyl. , -04 also means a thio7ene, pyridine, naphthalene or pyrene residue substituted with a nitro group,
Y is a hydrogen atom, cyanogen, or alkoxy. 1-o4 carbonyl group, optionally) fluorine-1 chlorine or bromine atom or alkyl. , -64, alkoxy 0l-Oa' nitro, amino-, monoalkyl cl -c4 amino- or dialkyl. 1-04 phenyl residue substituted by amino group or optionally quaternized and optionally) fluorine-1 chlorine- or bromine atom or alkyl-possible; alcohol, alkoxy o1-a, 'nitro, Cyanogen or alkyl carboxylate. , -04 ester groups substituted with thio7ene, benzothio7ene, 7rane, benzofuran, imidazole, pensoimitasole, thiazole, benzothiazole, oquinacyl or benzoxazole residue , 2 means a hydrogen atom or a carboxylic acid amide or cyan group, R is hydrogen-1 fluorine-
1 salt or bromine atom or alkyl, 1-04'alkoxy, nitro, amino, monoalkyl ol-c
In order to produce an abcoumarin represented by the general formula (2) (wherein X, R and n are A compound of the general formula (3) % (3) (I has the above meaning and 1 is cyano- or bromine atom) Alkoxy.1-84 carbonyl group) is condensed with a compound represented by the formula (4) obtained in this case by a method known per se (wherein, BXX, !, R and n have the above meanings). 80 to 14 with a non-oxidizing, aqueous mineral acid.
at a temperature of 0 DEG C. to form a compound of Z=H- in the general formula (1) above, and this is optionally reacted with a cyanide salt (by a conventional method), in which case the intermediate product The adduct formed as is simultaneously or subsequently treated with an oxidizing agent according to a method known per se to obtain a compound of the general formula (1) with g = Oll-o and this is optionally treated with an oxidizing agent according to methods known per se. In the method of general formula (1)
The above production method is characterized by saponifying to a compound of Z = Co-II (. - in the formula. 9 General formula (1) (wherein atoms or one or more alkyl τt-at'alkoxyal-c, 'cyan-, nitro-, amino-, monoalkylOx-C4-amino-, sial-amino-, monoarylamino-, diarylamino-,
Carbonyl-, carboxylic acid mido, carbon monoalkyl a, -C4 i-do, carbon dialkyl. , -04
amido-, alkoxy-at-at-carbonyl- or trifluoromethyl-substituted phenyl residues or in the case of chlorine- or bromine atoms or alkyl- or nitro-aK)-substituted thioene-, pyridine- , naphthalene- or pyrene residue, Y is a hydrogen atom or cyanide or alkoxy □1-a4 carbonyl group, optionally fluorine-1 chlorine- or bromine atom or alkyl □, alkoxy a, -04 phenyl residues substituted with at-C4, tridolphin, amino-, monoalkyl- or dialkyl- or optionally quaternized and optionally fluorine-1 Chlorine or bromine atom or alkyl. 1-0
4. Alkoxy. 1-04' nitro=, cyan-1 or alkyl carboxylate. , -04 ester group) substituted thio7ene-, benzothiophene-17ran-,
benzofuran, imidazole, benzimidazole, thiazole, benzothiazole, oxazole or benzoxazole residue), 2 means a hydrogen atom or a carboxylic acid amide or cyan group, R is hydrogen-1 fluorine -1 chlorine- or bromine atom or alkyl,
Alkoxy o1-o4'nido o, -'o4 0-, amino-, monoalkyl al-c4 amino-, dialkyl. , -o4 is an amino- or cyan group and n is a number of 1 or 2) mixed with a synthetic fiber material, in particular a linear polyester, in the case 1- or a natural fiber material. A method of acting as a dye for dyeing or printing. 1 (L fiber material cell day - Susie, -2μ- or -
10. A process according to claim 9, comprising a fibrous material of triacetate, polyamide, polyurethane, polycarbonate or polyethylene terephthalate, optionally mixed with cotton or wool. 1t General formula (1) (wherein X is optionally 1 or some fluorine-1 chlorine- or bromine atom or 1 or some alkyl-04'alkoxyc1-c4, cyan0, nido-, amino -, Monoalkyl. 1-04 Amino-, Sial: ?ko1-o4
Amino, monoarylamino, diarylamino
, carbonyl-, carbonamido-, carbonmonoalkyl□amido-, carbondialkyl l-04 Q, -c4amido-, alkoxy a1-a4carbonyl- or phenyl residue polysubstituted with trifluoromethyl group or in the case yoshichlorine or bromine atom or alkyl. 1-04 or thio7ene polysubstituted with nitro groups,
means pyridine-, naphthalene- or pyrene residue, Y
is a hydrogen atom or a cyanogen or alkoxyC, -C4 carbonyl group, optionally a fluorine-1chlorine or bromine atom or an alkyl group. , -041, a, alkoxy c1-c4' nitro, amino-, monoalkyl. 1-o4amino- or dialkyl. phenyl residues substituted by 1-o4 amino groups or optionally quaternized and optionally fluorine-1chlorine- or bromine atoms or alkyl. 1-a, "alkoxyloat-c4' nitro, cyanide or carboxylic acid alkyl ester group substituted with thio7ene, benzothio, phen-17rane, benzo7
Ran-, imidaglue, benzimidazole-, thiazole-1-zothiazole-, oxazole- or benzoxazole residue, 2 means a hydrogen atom or a carboxylic acid amide- or cyan group, R is hydrogen-1 fluorine-1 chlorine- or bromine atom or haalkyl 0. -0. '
Alkoxy σ1-04′ nido 0-, amino-, monoalkyl al-c4 amino-, dialkyl. 1”-('4
1. The use of azacoumarins represented by 'amino or cyan radicals and n#indicating the number i1 or 2) in melt-spinning dyeing of polyesters, neat coloring of synthetic resins or in light-harvesting systems. 5